Anthraquinonyl-dichloroquinoxaline dyestuffs



United States Patent "ce 3,251,844

Patented May 17, 1966 The organic residue W contained in the reactive group 3,251,844 I W ANTHRAQUINONYL-DICHLOROQUINOXALINE DYESTUFFS Josef Singer and Heinz Werner Schwechten, Leverkusen, 5

Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Gery, filial Elia, Contain l'fifl'ctive g estfirified many droxyl groups which :can readily split ofi, or activated ether 7 N0 P f W P l ll 1962, 2225937 or thioether groupings as reactive groups, as well as Claims I appllcatmn Germany P 23, 1961, carbon double and triple bonds which react with the cor- 12 Claims g responding reaction partners in the textile materials, e.g.

with the hydroxyl groups of the cellulose or the amide groups of natural fibres; The organic residue W, which exhibits at least one reactive group, may belong to the aliphatic, isocyclic and heterocyclic series. Suitable com- The present invention relates to novel anthraquinone dyestuffs; more particularly it relates to fibre-reactive anthraqumone dyestuffs of the formula 15 ponents for the introduction of this residue, which contain 0 at least two reactive substituents or groupings, are, inter l alia, 'dior tri-halotriazine compounds, such as dior 3033 tri-chloroor -bromo-sym.-triazines, alkyl or aryl-halogeno v I l triazine compounds, halocyanotriazines, halo-pyrimidines, Z S-cyano-halopyrimidines, as well as acyl compounds of I I 1} suitable carboxylic and sulphonic acid halides, for instance 0 NH- )n-a1ky1ene-N halogen-fatty acid halides, such as fi-chloroor ;3,[3di- 1 chloropropionic acid halide, furthermore derivatives of Y unsaturated aliphatic carboxylic acids, such as acrylic and methacrylic acid halides or mono-, d'ior tri-chloro- In the general formulae, R denotes hydrogen or on acrylic acid halides; other suitable compounds are 2,6- tlonaflly Substltuted afalkyl aryl residue; alkylene dich1oropyrimidine-4-carboxylic acid halides, 2,6-dichlorolower alkylene resldue having to 6 carbon atoms pyr'imidine-4-suiphonic acid halides, 2,3-dichloroquinoxy- 15 an lntegel' of 041 X b61115 a bond when n 18 O line-6-carboxylic acid halides or -sulphonic acid halides, and a member f as ammo: ethylene-sulphonic acid halides, and the like. amide, .carboxylannde, ether, or thioether groupings when For h preparation f the compounds (II), 4-bromo-1- n is 1; in both cases X is attached in meta or para position mnwanthraquinohgsulphonic acids, Which in addition with respect to the P P on the Phenyl Ting; V to a sulphonic acid group present in the 2-position may is hydrogen or Sulphomc acid group Y and Z are 9 contain a ifurther sulphonic acid group in the 5-, 6-, 7-, dl'ogen 'sllPstltuents P asjalkyl, alkoxy, P or 8-position, can be reacted at the aromatically bonded carboxylic acid or sulphomc acid groups, and W 1s an amino group with an aminohralkylamine, 6%. with an organic residue with at least one reactive group. W may aminohenzylamihe, sCh as 4 aminohenZy1 N methy1 be a straight'ichain branched alkylFne group amine; 3-aminobenzy1-N-butylamine, 4-am-inoberizyl-N- The dyestuffs are obtained when 1n dyestuifs of the 40 hhydroxyethylamine, or 4 amihodihehzylanihhe and the gene! 81 {formula resultant reaction product is sulphonated, if desired. The

O NH: position of the sul-fonic acid substituents which are intro- H duced into the amine component is not always exactly SOaH detectable; the sulphonation most probably results in a V I I mixture of isomeric monosulphonated products. The I a Z Y aminoarylalkylamine to be reacted may contain one to H six C-ato-ms in the alkylene chain in a straight chain, or i h L branched linkage. Examples are: l-(4-aminophenyl)- ethylamme-(Z); 1-(o-, m-, or p-aminophenyD-propyl-N- Y R (H) methylamine (3), 1-(3' aminophenyl)-butyl-N-rnethylamine-(3), 1-(o-, m-, or p-arninophenyU-S-methyl-3- the grouping methylamine-hexane.

Dyestuffs of Formula H in which X represents a bridging group are obtainable in similar manner as the above N indicated product Without bridge grouping, i.e. if X is a direct linkage. For producing the bridging member containing compounds 4-brorno-1-amino anthraquinone is Comm-ted into the reactive group sulphonic. acids may be condensed with N-methyl-N-fi- W methylamino ethyl-p-phenylene diamine, or N-methyl-N- -y-aminopropyl-p-phenylene diamine, or l-(4'-amino phenoxy) -butyl-N-methylamine-(4), or 1-(4'-amino-pheny1 mercapto) buty1-N-methylamine-4; or 1-(3-amino- I order to form h grouping phenylsulphonyl)-buty1-N-methylamine-(4).

The aryl residue of the aminoarylalkylamine may be W substituted by further substituents, such as alkyl or alkoxy groups or halogen. Examples of these are 2-methyl-5- aminobenzyl-N-rnethylamine, Z-methoxy-S-aminobenzylaniline, as well as 2-chloro-5-aminobenzyl=N-methylamine. the compound (II) is treated, by a method known as The novel f yestuifs are p rti ularly sllltable such, with a reactive at least bifunctional component condyeing and printing hydroxyl or am1de group-contain ng taining the residue W, for instance in a neutral'or weakly textile materials such as wool, silk, synthetic polyannde acidic medium. and polyurethane fibres, preferably for the production 3 of dyeings and prints on natural or regenerated cellulose. For this purpose, it is suitable to operate with acid-binding additives, where necessary with the aid of heat, in accordance with the methods commonly applied for reactive dyestuffs.

In the following examples, the .parts are parts by weight where not otherwise indicated.

Example 1v chloride solution, and the suction filtered residue is dried at 4050 C. The resultant dyestutf is a blue powder which dissolves in water with a blue colour. It has the structure:

50 g. of cotton yarn are preliminarily dyed at 40 C..

from a liquor which contains 2 g. of the resultant dyestuif per 1 litre of water. It is then warmed to 70-80 C. during 15 minutes with portionwise addition of 50 g. of sodium chloride. After a further 45 minutes 15 g. of soda are added, and it is dyed at 80 C. for another hour. After rinsing and soaping with boiling, a blue dyeing is obtained, with good wetting and light fastnesses properties.

Example 2 43.7 parts of the condensation product from 4-bromol-arnino-anthraquinone-Z-sulphonic acid and 4-aminobenzyl-N-methylamine as employed in Example 1 are dissolved in 150 parts of sulphonic acid monohydrate, sulphonated at utmost 35 C. by treatment with 70 partsof 20% SO -containing sulphuric acid, the sulfonation product is then dissolved at 30 C., in 500 parts of water, neutralized with soda lye and treated with 27 parts of 2,3-dichloroquinoxaline-6-carboxylic acid chloride, and the reaction mixture is m-aintained at a pH of 6-8 by the addition of sodium carbonate. after some time.

is obtained which is readily soluble with a blue colour. It has the following structure:

50 g. of cotton fabric are padded on a foul'ard with a solution, which contains 2 g./l. of the dyestufi, g./l. of Turkey red oil, g./l. of sodium carbonate, and 150 g./l. of urea. In order to prevent loss of moisture, the fabric is wrapped in a water-impermeable film, and after being left for 24 hours it is rinsed and soaped with boil- The reaction is completed. The reaction product is then isolated by the method described in Example 1. A blue powder ing. Deep blue dyeings with good wet fastness properties are obtained.

If in place of the above starting product, use is made of one from 4-bromo-1-aminoanthraquinone-Z-sulphonic acid, and 0-, mor p-aminobenzylN-methyl-amine or 3- or 4-arriinobenzyl-N-ethylor -N-butyl-amine or N-phydroxyethyl-a-mine, or 4-aminodibenzyl-amine, blue reactive dyestufi's are obtained which also exhibit good properties.

Example 3 44 parts of the sodium salt of 4-(4-aminoethyl-.phenylamino)-l-aminoanthraquinone-2eulphonic acid are sulphonated, and then reacted with 27 parts of 2,3-dichloroquinoxyline-G-carboxylic acid chloride as in Example 2. The resultant reactive dyestuti has the probable formula:

0 NH- CHz-GH -N\ H It dissolves in water with a blue colour, and dyes cotton in the presenceof alkaliand under, heat treatment fast blue shades.

Example 4 The condensation product from 4-bromo-l-amino-anthraquinone-Z-sulphonic acid and 1-(4'-aminopheny 1)- propyl-Nmethyl-amine-'(3) is sulphonated as in Example 2, and :acylated with 2,3-dichloroquinoxaline-dcarboxylic acid chloride. The resultant reactive dyestufi has the structure:

0 NH: II I l l SOgJNB SO Na (i NH orn-cm-o-Hn O 1411 It is readily soluble in water with a blue colour.

g. of cotton yarn is preliminarily dyed at 20 C.for a short time from a liquor which contains 2 g. of'the dyestuflf per 1 l. of water. Thereafter, it is heated to 40 C. during 20 minutes with portionwise addition of 50 g. of sodium chloride, and then with addition of 15 g. of sodium carbonate; the fabric is thereafter dyed at 40 C. for another hour. After thorough rinsing and soaping with boiling, there are obtained deep blue dyeings with very good wet fastness properties.

Example 5 The condensation product from 4-bromo-1-aminoanthraquinone-Z-sulphonic acid and 1-(3'aminophenyl)- butyl-N-methylamine-(3) is sulphonated, and acylated with the carboxylic acid chloride from Example 4. There is obtained a dyestuff of the structure:

I c 0 /N\ 01 SOsNa III-C Ha I i C un eal-o HC Hi N l I NH The product is readily soluble in water with a blue colourand yields blue dyeings with good fastnesses, when dyed according to the method stated in Example 4.

Example 6 The condensation product from 4-bromo-1-aminoanthraquinone-2-sulphonic acid and 1-(3'-aminophenyl)5- methyl-3-N-rnethyl-amino-hexane, after sulphonat-ion and acylation, produces the dyestuff of the structure:

V H CH:

SOsNa according to the method stated in Example 4. This produces fast blue dyeings, when employed according to the dyeing method of Example 4.

Example 7 Example 8 51.7 parts of the reaction product from 4-bromo-1- aminoanthraquinone-2,6-disulphonic acid and 4-aminobenzyl-N-methylamine are dissolved neutral by the addition of soda lye and are acylated with 27 parts of 2,3- dichloroquinoxaline-6-carboxylic acid chloride while using 1 N soda lye at pH 67.5. After completion of the reaction the resulting reactive dyestufi is precipitated with sodium chloride, filtered oil with suction, rinsed with aqueous sodium chloride solution, and the residue is dried at 40-50" C. The aqueous solution of the dyest-ufi dyes cotton fast blue shades after heat treatment in the presence of alkal'ies. The dyestufi? has the formula:

S OaNa NaSOa 4 CO l 3- N A dyestuff with similar properties is obtained if in place of the 4-bromo-1-aminoanthraquinone-2,6-disulphonic acid the isomeric 2,5-disulphonic is used.

Example 9 49.5 parts of 4-(4'-methylaminobutoxyphenylamino)- l-aminoanthraquinone-Z-sulphonic acid are sulphonated as in Example 2 and are acylated with 27 parts of 2,5-

6 dichloroquinoxaline-6-carboxylic acid chloride. The resulting dyestufi has the probable formula:

When dyed on cotton according to Example 1, it produces greenish blue shades'being fast to wet processing.

Example 10 51 parts of 4-(4'-methylaminobutylmercaptophenylamino)-l-aminoanthraquinone-Z-sulphonic acid are sulphonated as in Example 2 and are acylated with 2,3- dich1oroquin0xaline-6-carboxylic acid. The resulting dyestufl? has the probable formula:

(I) NHz In the heat, it dyes cotton from a weak alkaline bath I green-blue shades of good fastnesses.

Example 11 60.5 g. of the reaction product from 4-bromo-1-aminoanthraquinone 2,6 disulphonic acid and 4-(3'-aminophenylsulphonyl) -butyl-N-methylamine are acylated with 2,3-dichloroquinoxaline-6-carboxylic acid chloride as in Example 7. A dyestufi is obtained of the formula:

Example 12 18 parts of the sulphonated starting product obtained according to Example 2 from B-aminobenzyl-N-methylamine and 4-bromo-1-amino-anthraquinone-Z-sulphonic acid are dissolved in 200 parts of water at pH 6 and stirred, at 0 to 5 C., with a fine suspension, obtained by stirring an acetone solution of 6.2 parts of cyanuric chloride into 200 parts of ice water. By portionwise addition of 2 parts of soda, the mixture is thereby maintained at pH 6 to 7. After the condensation has been completed, the reaction product is precipitated with sodium chloride, isolated and washed with a solution of 11 parts of disodium phosphate in parts of water. It is dried in vacuo at 30 C. The resultant dyestulf corresponds to the formula:

n PNANJ1C I C Ha 7 8 It easily dissolves in water with a blue colour. 7 8. The dyestutf of the formula 50 g. of cotton yarn after being dyed at 20-25 C. for O 10 minutes in a dye liquor from 1.5 g. of the dyestuff II and 1 litre of water, are treated within 20 minutes with (\k 50 g. of disodium sulphate and subsequently with g. 5 I i of sodium carbonate (previously dissolved). It is thereafter dyed in the cold for another hour, rinsed thoroughly, H I

and soaped with boiling. The resultant blue dyeing possesses good fastnesses.

. N CHz-ifi-OC- on Example 13 503B 3 C C1 43.7 parts of the condensation product from 4-bromol-aminoanthraquinone 2 sulphonic acid and 4-aminobenzyl-N-methylamine are sulphonated and then dissolved The dyesnifi of the formula neutral at 10 C. in 500 parts of water with the addition of soda lye and acylated by stirring a saturated solution of 18 parts methoxydichloro triazine in acetone and 100 S0311 parts of 1 N soda lye. After the reaction has finished I i the resulting'dyestuff is precipitated with sodium chloride and isolated. It corresponds to the formula 20 l l N ,0 NHC n,1 I0c- NH:

CH3 l-Cl 0 I ()1 sour SOaNa A \Ny i i N N 5 Th 'dyestuff of the formula J 0C 0 NH: 00 N H: I g i A ILIH OH2N/\N so N\ G1 CHs CH3 Cl and dyes cotton fast blue shades according to the method i of Example 1.

We claim: sOaNa A dyesmfi of the formula 11. The-dyest-utf of the formula 00 1;:11: I NHz 01 soan soma on, v i l l Z on on 'cncn 011-021 I Y V 2a 2- 2' t O NH- (X) n-al ylene d l IH C H Y SOaNa 12. The d estufi of the formula wherein V stands for a member selected from the class y consisting of hydrogen and .a sulphonic acid group, Y

(|) NH, stands for a member selected from the class consisting so W of hydrogen, lower alkyl, lower alkoxy, chloro and a 5 a 00 N sulphonic acid group, Z stands for a member selected N Os C1 from the class consisting of hydrogen, lower alkyl, lower a 3 SOHCHZ) alkoxy, chloro and a sulphonic acid group, n is an intger l Q C 3 C1 of 0-1, and X is a member selected from the class con- N sisting of meta-substituted -SO -O- and S-,

and parwsu'bstimted and when n References Cited by the Examiner is l, and a similarly placed direct carbon-carbon linkage UNITED STATES PATENTS Between the alkylene and Phenyl groups when n is 0; 2,167,804 8/1939 Gubler et a1 260249 alkylene means a lower alkylene group and R stands 2,773,871 12/1956 Brassel et a1 for a member selected from the class consisting of hy- 7 2,907,762 10/1959 Heslop 260-249 drogen, lower alkyl, hydroxy lower alkyl and benzyl. 2 952 690 9/1960 Riat 2. A dyestnfi of claim 1 wherein R stands for methyl. 3t). Ahdyelstutf (I); claim 1 wherein alkylene stands for FOREIGN PATENTS a s ra1g c am a yene'group.

315,451 7/ 1929 Great Britain. 4. A dyestutf of claim 1 wherein alkylene stands for 854,432 11/1960 Great Britain.-

-CH 5. A dyestuff of claim 1 wherein V stands for hydrogen. WALTER MOD ANCE Primary Examiner I 6. A dyestnif of claim 1 wherein Z stands for hydrogen. 7. A dyestuff of claim 1 wherein Y stands for a sul- NICHOLAS RIZZO, JOHN M- 79 FORD, Examiners.

phonic acid group.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 251, 844 May 17, 1966 Josef Singer et alc It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 26, for "on" read M an column 4, lines 40 to 48, the formula should appear as shown below instead of as in the patent:

O NH H i 2 I I O Na C C1 H ca -ca -CH N l O 2 2 2 CH column 5, line 39, for "alkyline" read alkaline column 7, lines 36 to 45, the formula should appear as shown below instead of as in the patent:

0 EH8 R Signed and sealed this 22nd day of August 1967 (SEAL) Attest:

ERNEST W. SWIDER EDWARD JJ BRENNER Attesting Officer Commissioner of Patents 

1. A DYESTUFF OF THE FORMULA 